Method of treating wool-containing textile materials



Patented July 11, 1950 UNITED STATES PATENT OFFICE 2. 15.107 METHOD OFTREATING WOOL-CONTAINING TEXTILE MATERIALS ChcsterLAmichBonndMH-JlIIignor-to American Cyanamid New; York, N. Y.. a corporation of MaineNo Drawing. Application March 8813! No. 13,074 1 Claim. (Cl. 11'I133-5)The present invention is directed Specifically to a method of renderinga woolen textile material resistant to shrinking and to attack by carpetbeetle larvae which comprises first impregnating the said textilematerial with an impregnating composition consisting of an aqueoussolution of methylated methylol melamine containing a small amount ofboth diammonimn hydrogen phosphate and hexamethylene tetramine. In thissolution the diammonium hydrogen phosphate is present therein in a majorproportion with respect to the hexamethylene tetramine. Furthermore, thesolution has dispersed throughout an acetone solution of a 1.1-bis-(chlorinated phenyl) -2,2-dichloroethylene, the chlorinated phenylgroups of which contain an average of two chlorine atoms for each phenylnucleus. Also, the said 1,1-bis- (chlorinated phenyl)-2,2-dichloroethylene is present in the impregnating composition in aweight ratio of about 1 part thereof to about parts of the saidmethylated methylol melamine on a net dry basis. After the textilematerial has been impregnated with the aforesaid impregnatingcomposition, the impregnated textile is squeezed so that it retainsabout 100%, by weight of the dry textile, of the impregnatingcomposition. Thereafter the squeezed textile material is dried and,finally, the dried textile material is heated at a temperature ofapproximately 285 F. to convert the said methylated methylol melamine,while intimately associated with the said i,1-bis(chlorinated phenyl)-2,2- dichloroethylene, to a substantially water-insoluble condition.

The embodiment of my invention involving a textile-treating orcomposition or agent is concerned with such a treating material whichcomprises an intimate and homogeneous association of ingredientscomprising (1) an aikylated methylol melamine which is at least partlysoluble and preferably substantially completely soluble in water, e. 3.,a water-soluble methylated methylol melamine, more particularly awater-soluble methylated polymethylol (dimethylol, trimethyloi, etc.)melamine. and as (2) a compound (or mixture 01' compounds) representedby the general formula.

wherein R represents a member of the class consisting oi chlorine andbromine, R and R" each represents a. member 01 the class consisting ofhydrogen, chlorine. bromine, alkyi (e. 3.. methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec.-butyl, amyl to octadecyl, inclusive,etc.) and alkoxy (e. g., methoxy, ethoxy. propoxy. isopropoxy, butoxy,isobutox sec-butoxy. nentoxy to octadecoxy, inclusive. etc.), and nrepresents one of the integers l and 2. e. g., a 1,i-bis(dichlorophenyl)-2,2-dlchloroethylene. a 1,1-dixylyl- 2,2-dichloroethylene, which about0.05 to about or (2) for each part alkylated methylol melamine of (1).Such textile-finishing agents are especially adapted for rendering awool-containing textile material, e. 3., a woolen cloth or other fabric,re sistant to shrinking and to attack by moths and other insects. Thewool-containing textile is impregnated with a combination, as in theform of an aqueous liquid composition (e. 3., aqueous dispersion)alleviated methylol melamine and a diaryldihalogenoethylene (or melamineplus the diaryidihalogenoethylene compound or compounds which is appliedto the textile material is such that the ilnlshed textile contains from2% (about 2%) to 25% (about 25%), more particularly from 4 to 20 or 25%(about 4 to about 20 or 25%), by weight of the dry textile, of animpregnant comprising cured alkylated methylol melamine, curedmethylated methylol melamine, in combination (more particularly in theform a homogeneous association) with a diaryldihalogenoethylene of thekind embraced by Formula I or with a mixture of such compounds. Thescope of the invention also includes the products resultin from thetreatment of wool-containing textile materials with textile-finishingcompositions or agents of the kind briefly described above.

A number of contact insecticides have been used heretofore formothprooiing purposes, some of the most eflectlve being condensationproducts of an aromatic hydrocarbon, e. 3., bennene, with chloral orchloralhydrate. Such insecticides are described, for example. in PatentNo. 232933- Milller. Oneof thebestknownofthisclassof as "D. D. T.," thechemical name of which is dichlorodiphenyltrichloroethane. Another classof contact insecticides which are suitable for many purposes for which"D. D. T." and others of the aforementioned class are insumcientlyactive are diaryldihalogenoethylenes of the kind idal componand Chestera Amick, serial No. 610,666, illed August 13, 1945, and now abandoned,are discomprising an aqueous solution of an alkylated methyioi melaminehaving suspended therein a finely divided, water-insoluble insecticideof the class exemplified by dichlorodiphenyltrichloroethane, thealkylated methylol melamine and the said insecticide being employed incertain particular proportions, and a method of finishing woolentextiles which involves treating the textile with such a finishingcomposition. Widmer et al. Patent No. 2,318,121 discloses compositionscomprising an aminotriaaine-aldehyde condensation product as a binderfor fungicidal or insecticidal dusting agents which are to be sprayedupon a surface to be protected.

Theuseofinsecticidesofthekinddisclosed in the aforementioned Mullerpatents for mothprooiing and similar purposes has presented a dimcultproblem, since such insecticides are insoluble in water and do notadhere readily to textiles. Application of such insecticides to textilesby impregnating the textile with a solution oi the compound in acetoneor other volatile solvent, followed by removal of the solvent from theimpregnated textile, has shown that the active insecticidal material isdusted from the surface of the textile and is completely removed whenthe textile is laundered.

The present invention has as a principal object the provision oftextile-finishing compositions containing (1) a diaryldihalogenoethylene(or mixture of diaryldihalogenoethylenes) of the kind embraced byFormula I and (2) a curable or potentially curable resinous material.the proportions of the components of (1) and (2) being such that theinsecticide is adhesively and eilec- 4withinitsintersticeswhentheresinitseliis cured to a water-insolublestate, whereby a laundry-resistant ilnish is imparted to the textile.

Another object of the invention is to providesolutionsordispersionsofthlstypeinwhiehthe resinous binder for theinsecticide imparts shrinkage control to the impregnated textilematerial. whereby the finished textile is rendered resistant, even afterrepeated launderlngs, both to the attack of insects and insect larvae(including carpet beetle larvae) and, also, to shrinkage. Still furtherobjects of the invention are the provision of methods of imparting theaforementioned properties to woolen or wool-containing textiles by theuse of the above-described finishing compositions and the products ofsuch methods.

The foregoing and other objects are attained as briefly described in thesecond and third paragraphs of this specification and more fullyhereafter. I have found that compositions capable of imparting shrinkacontrol and insecticidal properties, specifically mothprooflnproperties, to wool-containing textila, which properties are retainedcompletely or substantially completely even after repeated launder-inns,are obtained by dispersing or otherwise uniformly incorporating adiaryldihalogenoethylene of the kind embraced by Formula I in an aqueouscomposition containins an alkylated or alcohol-reacted methylolmelamine, which is at least partly soluble in water and which,preferably, is substantially completely soluble in water, for instance awater soluble methylated methylol melamine.

The application to woolen textiles of aqueous alkylated metbylolmelamine solutions or disperslons for thepurpose of reducing the feltingand shrinking tendencies of the woolen textile is described lnJohn-stone at al. Reissue Patent No. 22,566. and is now in widecommercial use. The present invention is based on my discovery that whena wool-containing textile material is impregnated with such an alkylatedmethylol melamine and a diaryldlhalogenoethylene of the kind with whichthis invention is concerned, within a particular range of proportions ofeach, and when the aforementioned combination of impregnants is presentin the treated textile in an adequate amount. the impregnated textilematerial is rendered not only resistant to felting and shrinking butalso to attack by insect larvae, specifically carpet beetle larvae, evenafter repeated launderings. Furthermore, the insecticide does not dustof! the textile. These results were quite surprising and unexpectedsince ordinarily it would be expected that insolubillsation of thealirylated methylol melamine by curing would mask the ability of thediaryldihalosenoethylene to function as an insecticide; also, itnormally would be expected that the added diaryldihalogenoethylene,which by itself is not able to impart shrinkresistant characteristics toa wool-containing textile material, would adversely affect the abilityof the alkylated methylol melamine to reduce the felting and shrinklnstendencies of such a textile. contrary to expectations the alkylatedmethylol melamine and the diaryldihalogenoethylene coact uponapplication to woolen textiles, and the like, of an aqueous solution ofthe alkylated methylol melamine having the diaryldihalogenoethylenedissolved or therein. followed by heating the impregnated textilensolubilize the resin therein.

The substantially completely water-soluble tively bonded to the surfacesof the textile and 7s alkylated, specifically methylated, methylolmelamines provide optimum results in carrying my invention into effect,and. therefore are preferred. They may be prepared as described, forinstance, in the aforementioned Johnstone et al. Reissue Patent No.22,566. Thus a methylated methylol melamine may be produced by effectingreaction under acidic conditions between a polymethylol melamine andmethyl alcohol in the ratio of 1 mol of the former to from 2 t0 6 molsof the latter, depending upon the number of methylol groupings in themelamine derivative and the extent of methylation (or etheriflcation)desired. The reaction is stopped before the product becomes hydrophobic,alkali is added in an amount at least suilicient to neutralize the mass,after which the mass is dehydrated under vacuum. The preierredmethylated methylol melamines, more particularly poly-(methoxymethyl)melamines, are miscible with water in all proportions at roomtemperature and are stable on storage at 120 F. for at least two weeks.

A more detailed description of the preparation of a substantiallycompletely water-soluble, heatcurable or thermosetting, methylatedpolymethylol melamine which is especially suitable for use in practicingmy invention follows: a

One mol of melamine is mixed with 3.3 mols of aqueous 37% formaldehydepreviously adjusted to a pH of approximately 8.0, the temperature beingraised to 70 C. and maintained at this point until a clear solution isobtained. The solution is then immediately cooled and allowed to set,after which the mass is broken into small pieces and dried bycirculating warm air at a temperature not exceeding 55 C. The resultingdried powder is alkylated by admixture with twice its weight of 95methanol containing 0.5% of oxalic acid crystals, based on the weight ofthe methylol melamine. The mixture is heated to 70 C. and held at thistemperature for approximately minutes, or until a clear solution isobtained, whereupon it is immediately neutralized by the addition ofsufficient sodium hydroxide solution to raise the pH to approximately9.0. The neutralized reaction mass is then evaporated to 80% solidsunder reduced pressure so that the temperature does not rise above 50 C.

The diaryldihalogenoethylenes used in practicing my invention aredescribed, including a general method of preparing the same, in theaforementioned Miiller Patent No. 2,429,839. Illustrative examples ofsuch compounds are:

Other examples are given in the aforesaid Milller patent, includingcompounds corresponding to the formulas:

omoQi-Q-ocm mmoOcG-ocm.

Ellis BrQiQ-OQH 1,1-bis(2',3' dichlorophenyl) 2,2 dichloroethylene1,l-bis(2',4'-dichlorophenyl) 2,2 dichloroethylene1,1-bis(2,5'-dichlorophenyll 2,2 -dichloroethylene1,1-bis(2',6'-dich1orophenyl) 2,2 dichloroethylene 1,1-bis(3',4'dichlorophenyl) 2,2 dichloroethylene l,1-bis(3',5' dichlorophenyl) 2,2dichloroethylene 1-(2',3' dichlorophenyl) 1 (2",4" dichlorophenyl)-2,2-dichloroethylene 1-(2',4' dichlorophenyl) 1 (2",6" dichlorophenyl)-2,2-dichloroethy1ene 1- (2,5'-dichlorophenyl) -1- (3' ',4''-dichlorophenyl) -2,2-dichloroethy1ene 1,1-bis(2',3'-dimethylphenyl)2,2 dichloroethylene 1,1-bis(2',4'-dimethylphenyl) 2,2 dichloroethylene1,1-bis(2',5'-dimethylpheny1) 2,2 dichloroethylene1,1-bis(2',6'-dimethylphenyl) 2,2 dichloroethylene1,1-bis(3',4'-dimethylphenyl) 2,2 dichloroethylene1,1-bis(3',5'-dimethylphenyl) 2,2 dichloroethylene l-(2,4'-dimethylphenyl) -l- (2 ,5'-dimethylphenyl) -2,2-dichloroethylene1- (2',3'-dimethylphenyl) 1- (3,4 -dimethylphenyl) -2,2-dichloroethylene1- (2,6'-dimethylphenyl) -1 (3 ',5' -dimethylphenyl)-2,2-dich1oroethy1ene Mixtures of isomers of a 1,1-bis(dichlorophenyl)2,2-dichloroethylene or of a 1,1-(dimethylphenyl)-2,2-dichloroetlrvlenemay be used if desired.

In preparing the textile-finishing compositions used in practicing myinvention, the diaryldlhalogenoethylene is incorporated in any suitablemanner into the aqueous solution or dispersion of the alkylated methylolmelamine in an amount such that the proportions of the two ingredientsare within the range hereinbefore mentioned. Thus, the finely dividedinsecticide may be dispersed,

as by thorough agitation, in the alkylated methylol melamine to form ahomogeneous composition, using a suitable dispersing agent to aid in theformation of the homogeneous dispersion. Preferably, however, thediaryldihalogenoethylene is first dissolved in a suitable solvent, e.g., alcohol, acetone, petroleum naphtha or other petroleum solvent,etc., and the resulting solution is then dissolved or dispersed in theaqueous solution or dispersion of the aikylated methylol melamine. Iprefer to use a solvent, such for instance as alcohol or acetone, whichis miscible with water. as the solvent for dissolving the insecticide.Any of the conventional dispersing agents. e. g., dioctyl sodium sulfosuccinate, isopropylnaphthalene sodium sulfonate, etc., may be used infacilitating the dispersion of the finely divided insecticide orsolution thereof in the aqueous liquid composition comprising a solutionor dispersion of the alkylated methylol melamine. The insecticide, ifdesired, also may be first emulsified with water, and the resultingemulsion then may be incorporated, as by thorough agitation, in thesolution or dispersion of the alkylated methylol melamine.

After producing a homogeneous composition containing the alkylatedmethylol melamine and the diaryldihalogenoethylene, more particularly aliquid composition comprising an aqueous solution of the aforementionedalkylated methylol melamine having dispersed therein an insecticide ofthe kind with which this invention is concerned, the resulting aqueouscomposition may be diluted with water, as desired or as may be required,in order to obtain a finishing composition having the concentration ofsolids desired for textile application. For example, the concentrationof solids in the aqueous composition may be, for instance, from 2 to 40or 45% (about 2 to about 40 or 45%) by weight of the composition,depending, for example, upon the method of expression or squeezing ofthe wet, impregnated textile. Ordinarily, however, the alkylatedmethylol melamine and the diaryldihalogenoethylene together constitutefrom about 4 or 5% to about 30 or 35% by weight of the finishingcomposition.

In order to speed up the curing of the alkylated methylol melamine or todecrease the heatin time a suitable catalyst may be added, if desired,to the aqueous composition, e. g., oxalic acid, acetic acid, phosphoricacid, diammonium hydrogen phosphate, diammonium ethyl phosphate,diammonium phthalate, ammonium chloride, ammonium silicofluoride, amelamine fluosilicate, a melamine iluoborate, and others which are knownto be catalysts for curing modified or unmodified melamine-formaldehydereaction products including the alkylated methylol melamines. The amountof catalyst may be varied as desired or as conditions may require, butordinarily the catalyst is employed in an amount corresponding to from0.5 to 5% by weight of the alkylated methylol melamine.

The textile-finishing composition comprising an aqueous solution ofalkylated methylol melamine, e. g., water-soluble methylated methylolmelamine, having dissolved or dispersed therein adiaryldihalogenoethylene of the kind embraced by Forumla I shouldcontain the latter in a weight ratio of from 0.05 to 1 part, c. g., from0.05 to about 0.6 or about 0.7 part, of the said salt for each part ofthe alkylated methylol melamine in order to obtain satisfactory results.If less than 0.05 (about 0.05) part of the diaryldihalogenoethylene beemployed for each part of the alkylated methylol melamine, the finishedtextile will not be rendered adequately resistant to at tack by variousinsects and insect larvae including carpet beetle larvae. on the otherhand, if substantially more than 1 part. say, 2 or 3 or more parts, ofdiaryldihalogenoethylene be used for each part of the alkylated methylolmelamine, a considerable amount of the insecticide is removed from thetextile upon repeated iaunderlngs and is economically undesirable. Goodresults are obtained when the alkylated methylol melamine constitutes,by weight, a major or larger proportion and the diaryldihalogenoethylenea minor or lesser proportion of the mixture of the two. e. g., from, byweight, 55 to (about 55 to about 95%) of the former to from 45 to 5%(about 45 to about 5%) of the latter.

Other adiuvants may be added to the textilefinishing composition asdesired or as conditions may require. These may include bufferingagents, e. g., hexamethylene tetramine, or other agents which will bringthe composition to the particular pI-I desired for application of thecomposition to the textile material to be treated. The composition maybe adjusted so that it is either alkaline, neutral or acid as it isapplied to the woolen fabric or other wool-containing textile. Thetextile-finishing composition also may contain pigments, dyes,softeners, penetrating agents or other insecticides, bacterlcides orfungicides, or other adjuvants employed in textile-finishing materialsincluding surface-active agents, e. g., dloctyl sodium sulfo succinate,isopropylnaphthalene sodium sulfonate, etc.

When the woolen fabric or other wool-containing textile material isimpregnated with by weight of the dry textile, of the textile-finishingcomposition, the impregnated textile will contain, after drying andcuring of the alkylated methylol melamine, approximately the samepercentage of cured resin admixed or combined with thediaryldihalogenoethylene as the percentage of alkylated methylolmelamine and diaryldihalogenoethylene which is present in thetextile-finishing composition.

The alkylated methylol melamine and dlaryldihaiogenoethylene may beapplied to the wool-containing textile material in various ways. Forexample, if the alkylated methylol melamine and diaryldihalogenoethyleneare applied in the form of an aqueous solution or dispersion containingthe same, the dry or substantially dry textile to be treated may beimmersed in the aqueous composition and then passed through pressurerolls, mangles or centrifugal extractors to secure uniform impregnationand a controlled removal of the excess material. The fabric or othertextile, however, may be impregnated by other methods. e. g., byspraying.

The pick-up of the aqueous finishing composition by the wool-containingtextile material should be adjusted so that the finished textilecontains from 2 to 25% (about 2 to about 25%). more particularly from 4,5 or 6 up to 15, 20 or 25%, by weight of the dry textile, of the curedalkylated methylol melamine admixed or otherwise combined with theaforementioned diaryldihalogenoethylene. The proportions of theseingredients in the finished textile will be of the same general order asthe proportions of the alkyiated methylol melamine anddiaryldihalogenoethylene in the textile-finishing composition as appliedto the textile. The amount of the aqueous finishing composition pickedup by the textile, that is, the so-called "wet pick-up." may be variedas desired or as conditions may require and may range. for example, fromabout 40 or 50% up to about 150% or more by weight of the dry textiledepending, for example, upon the particular textile treated, method andconditions of treatment, concentration oi solids in the impregnatingbath, amount of solids and properties desired in the finished textile,etc

The wet, impregnated woolen fabric or other wool-containing textilematerial is then dried and cured. The drying and curing temperatures maybe varied considerably, but ordinarily temperatures within the range of160 F. (about 160 F.) to 400 F. (about 400 F.) are employed. Theimpregnated textile may be dried at a relatively low temperature of theorder of 160 1''. to 212 F. to remove all or most the water and anyother low-boiling solvent (e. g., water, alcohol, etc.) which may bepresent. after which the dried material is heated at a temperaturewithin the range of 250 F. to 400 F. (about 250 F. to about 400 F.) toconvert or cure the curable alkylated methylol melamine admixed with theaforementioned diaryldihalogenoethylene insecticide to a substantiallywater-insoluble condition. As a result of this heat-curing of thealkylated methylol melamine in the presence of the said insecticide,which is an ethylenically unsaturated compound, the latter becomes fixedby the cured methylol melamine derivative and may chemically combine, e.g., by means of a copolymerization reaction through the double bond ofthe diaryldihalogenoethylene, with the alkylated methylol melamine,thereby forming in situ a resinous complex which functions to impartboth shrinkage resistance and resistance to attack by various insectsand insect larvae, specifically carpet beetle larvae, to the treatedtextile. That such a reaction actually does take place is supported byother known facts, for instance the outstanding washi'astness of thetreated textile and the fact that it is known that ethylene andsubstituted ethylenes can be caused to undergo polymerization andcopolymerization reactions.

The drying and curing operation is flexible and may be varied to suitthe available equipment. Continuous methods are preferred. However,drying and curing also may be effected by framing the impregnated fabricto width, as on a in tenter, drying the framed fabric, batching it upona shell and then allowing it to stand hot for a period suflicient toconvert the solid impregnant in situ to a water-insoluble state. In somecases drying and curing for 2 or 3 hours at 200 F. may be required.Heating the dried fabric at higher temperatures ranging from a fewseconds to a few minutes at higher temperatures of the order of 250 F.to 400 F. may be employed, the shorter periods being used at the hi hertemperatures.

After the woolen fabric or other woolcontaining textile material hasbeen treated as above described, it may be given a mild soapingtreatment to render it softer and more pliable. It then may be given theusual finishing treatments such as decatizing, brushing, shearing,pressing, etc. My process may be applied to colored goods as well as towhites without appreciably affecting the color or shade and withoutdamage to the material.

In order that those skilled in the art better may understand how thepresent invention may be carried into eifect. the following examples are10 given by way of illustration and not by way of limitation. All partsand percentages are by weight.

Example 1 Forty-five parts of aqueous methylated methylol melaminecontaining about 80% of solids was diluted with 200 parts of water, towhich was then added about 50 parts of an aqueous solution containingabout 2.3% thereof of diammonium hydrogen phosphate and about 0.3% ofhexamethylene tetra-mine. To the resulting solution was added. withvigorous agitation, 50 parts of a 7% acetone solution of a1,1-bis(cblorlnated phenyl)-2,2-dichlorethylene. The chlorinated phenylgroups contained an average of two chlorine atoms for each phenylnucleus. This composition was composed mainly of a 1.1-bis(dichlorophenyl) 2,2 dlchloroethylene, the chlorine atoms presumablybeing in the ortho and para positions. The insecticide was dispersedthroughout the resin solution in the form of a line, milky suspension.

Two 12-inch all-wool flannel squares, each weighing about 35.5 grams,were immersed in the textile-finishing composition prepared as abovedescribed, and then were passed through squeeze rolls adjusted so thatthe fabric retained about by weight oi the dry fabric, of theimpregnating composition. The impregnated pieces were dried first atabout F. and then heated at approximately 285 F. to cure the methylatedmethylol melamine to a water-insoluble condition.

One of the treated pieces was washed iive times by a standard launderingprocedure as outlined on pages 225-226 of the 1943 Year Book 0'! theAmerican Association of Textile Chemists and Colorists. After thistreatment the treated sample showed a shrinkage of 6% in the warp and2.3% in the filling, as compared with a shrinkage of 35% in the warp and51% in the filling for the untreated woolen material when washed fivetimes by the same laundering procedure.

The treated pieces, both washed and unwashed, were then evaluated forinsecticidal and mothproofing properties by exposure to the action ofblack carpet beetle larvae, using the method recommended in thepublication, Soap and Sanitary Chemicals, vol. 18 (August, 1942), pages95-418. The corrected weight of the droppings of the treated butunwashed sample was 0.0 mg. after exposure for two weeks. The correctedweight of the droppings from the treated sample which had been washedfive times was also 0.0 mg. after two weeks exposure, thus showing thatthe insecticidal properties of the piece were retained even afterrepeated washings. An untreated piece of the same flannel which hadreceived five washings showed a corrected weight of 21.4 mg. ofdroppings after two weeks exposure to the black carpet beetle larvae.

Example 2 Same as Example 1 with the exception that a mixture of isomersof 1,1-bis(dimethylphenyl)- 2,2-dichlororoethylene was used instead ofthe insecticide of that example. After being washed live times, thetreated sample showed a shrinkage of 5% in the warp and 14.6% in thefilling. The treated pieces, both washed and unwashed, also showed goodinsecticidal and mothprooflng properties. the corrected weight of thedroppings of I! the treated but unwashed sample being 0.0 mg. afterexposure for two weeks to the black carpet beetle larvae.

Example 3 Same as Example 1 with the exception that1:1-diphenyl-2,2-dichloroethylene was employed in place oi theinsecticide of that example. After five launderings the treated sampleshowed a shrinkage oi in the warp and, also. in the filling. Theresistance of the treated pieces, both washed and unwashed, to theaction of black carpet beetle larvae was less than that of the treatedfabrics of the previous examples wherein diil'erent insecticides wereused. The corrected weight of the droppings of the treated but unwashedpiece was 1.3 mg. while that of the treated, washed sample was 5.9 mg.,after each was exposed for two weeks to the carpet beetle larvae, ascompared with a corrected weight of 21.4 mg. of

droppings for the untreated piece after flve wash-' logs.

The present invention provides a rapid, economical and convenient meansof rendering a wool-containing textile material resistant to shrinkingand felting and, also, to attack by insects, e. g., the common carpetbeetle, the furniture carpet beetle, the tapestry moth, the casemakingclothes moth, the webbing clothes moth. and other insects which attackwool-containing and other textiles. The treated textile is resistant todry cleaning and soaping or other washing. cleaning or launderingoperations; that is, the insecticide is so bound, possibly by chemicalreaction, that it is not easily or readily removed, if at all, when thefabric is washed or otherwise cleaned. Furthermorathe insecticidalaction of the diaryidihalogenoethylene continues to prevail even thoughit is homogeneously distributed throughout, or imbedded in, or otherwisecombined with, a resin, specifically a cured alkylated methylolmelamine, which itself is resistant to laundering and is capable ofimparting shrinkage resistance to the wool-containing textile material Iclaim:

The method 01 rendering a woolen textile material resistant to shrinkingand to attack by carpet beetle larvae which comprises (1) impregnatingthe said textile material with an impregnating composition consisting ofan aqueous solution of methylated methylol melamine containing a smallamount 0! both diammonium hydrogen phosphate and hexamethyienetetramine. the said phosphate being prmnt in the said solution in amajor proportion with respect to the said hexamethylene tetramine. andthe said solution having dispersed throughout an acetone solution of a1,1 bisichlorinated phenyl 2.2 dichloroethylene. the chlorinated phenylgroups of which contain an average of two chlorine atoms for each phenylnucleus, and the said dichloroethylene being present in the saidimpregnating composition in a weight ratio of about 1 part thereof toabout 10 parts of the said methylated methyiol melamine on a net drybasis, (2) squeezing the impregnated textile material so that it retainsabout by weight of the dry textile, of the said impregnatingcomposition, (3) drying the squeezed textile material and finally (4)heating the dried textile material at a temperature of approximately 285F. to convert the said methylated methyiol melamine, while intimatelyassociated with the said dichloroethylene, to a substantiallywater-insoluble condition.

CBI'BTER A. AMIC'K.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATE PATENTS Number Name Date Re. 22,566 Johnstone Nov. 21. 19442,318,121 Widmer May 4, 1943 2,429,839 Muller Oct. 28, 194'!

